US4892576A - 6,7-dihydro-pyrazolo (1,5-A)(1,3,5)triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators - Google Patents
6,7-dihydro-pyrazolo (1,5-A)(1,3,5)triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators Download PDFInfo
- Publication number
- US4892576A US4892576A US07/213,905 US21390588A US4892576A US 4892576 A US4892576 A US 4892576A US 21390588 A US21390588 A US 21390588A US 4892576 A US4892576 A US 4892576A
- Authority
- US
- United States
- Prior art keywords
- group
- alkyl
- phenyl
- triazine
- halo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004009 herbicide Substances 0.000 title abstract description 7
- CBZTZOURYPCRBA-UHFFFAOYSA-N 6,7-dihydropyrazolo[1,5-a][1,3,5]triazine-2-sulfonamide Chemical class C1=NC(S(=O)(=O)N)=NC2=CCNN21 CBZTZOURYPCRBA-UHFFFAOYSA-N 0.000 title description 4
- 239000005648 plant growth regulator Substances 0.000 title description 4
- 230000008635 plant growth Effects 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 47
- 241000196324 Embryophyta Species 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- -1 sulphonyl group Chemical group 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 16
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 230000002363 herbicidal effect Effects 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 239000000969 carrier Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 3
- 125000001424 substituent group Chemical group 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 229940124530 sulfonamide Drugs 0.000 description 40
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- 239000002904 solvent Substances 0.000 description 17
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- 230000000694 effects Effects 0.000 description 7
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
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- 150000002905 orthoesters Chemical class 0.000 description 5
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- VMDZMIRQMJSNDP-UHFFFAOYSA-N methyl 3,3-bis(benzylsulfanyl)-2-cyanoprop-2-enoate Chemical compound C=1C=CC=CC=1CSC(=C(C#N)C(=O)OC)SCC1=CC=CC=C1 VMDZMIRQMJSNDP-UHFFFAOYSA-N 0.000 description 3
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- ASTWHKAFJCZAPX-UHFFFAOYSA-N methyl 3-benzylsulfanyl-1-(methylcarbamothioyl)pyrazole-4-carboxylate Chemical compound CNC(=S)N1C=C(C(=O)OC)C(SCC=2C=CC=CC=2)=N1 ASTWHKAFJCZAPX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Definitions
- the invention relates to new 6,7-dihydropyrazolo-[1,5-a][1,3,5]triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators.
- the object of the present invention is to make new compounds that do not show the disadvantages of the known compounds and have improved biological properties.
- R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy, halo-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halo-C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulphinyl or C 1 -C 4 -alkylsulphonyl, halogen, C 1 -C 4 -alkoxy, a group R 10--O--CO , a carbamoyl group R 11 R 12 N--CO--, an amino group R 11 R 12 N--, cyano, nitro, a sulph
- R 6 is hydrogen, an acyl group R 10 --CO, a group R 10 --O--CO--, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl-C 1 -C 4 -alkyl, a carbamoyl group R 11 R 12 N--CO--, an alkali metal atom, a single metal equivalent of an alkaline earth or other metals or ammonium group, optionally substituted by C 1 -C 6 -alkyl,
- R 7 and R 8 are the same or different and are hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo and/or C 1 -C 4 -alkoxy, a phenyl-C 1 -C 6 -alkyl, phenyl-C 2 -C 6 -alkenyl or phenyl-C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or halo-C 1 -C 4 -alkyl, phenyl, substituted by R 1 , R 2 , R 3 , R 4 and R 5 , an acyl group R 10 --CO,
- R 9 is hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo and/or C 1 -C 4 -alkoxy, a phenyl-C 1 -C 6 -alkyl, phenyl-C 2 -C 6 -alkenyl or phenyl-C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or halo-C 1 -C 4 -alkyl, phenyl, substituted by R 1 , R 2 , R 3 , R 4 and R 5 , an acyl group R 10 --CO, a group R 10 --O--
- R 10 is hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or phenyl-C 1 -C 4 -alkyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C 1 -C 4 -alkoxy, or phenyl, optionally substituted by halo, nitro or C 1 -C 4 -alkyl,
- R 11 and R 12 are the same or different and are hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C 1 -C 4 -alkoxy, or
- R 11 and R 12 together with the adjacent nitrogen form a pyrrolidinyl, piperidino or morpholino ring,
- X is oxygen or sulphur
- n 0, 1 or 2
- halogen in relationship with alkyl, alkenyl, alkynyl or phenyl means that one or more hydrogen atoms are replaced by one or more halogen atoms.
- halogen means fluorine, chlorine, bromine and iodine.
- Ar is a phenyl group of general formula ##STR4##
- R 1 and R 5 are the same or different and are halogen, methyl, trifluoromethyl, nitro, methoxy or methoxycarbonyl,
- R 2 , R 3 and R 4 are the same or different and are hydrogen, halogen, trifluoromethyl or a C 1 -C 4 -alkyl group,
- R 6 is hydrogen, a single equivalent of a metal or a C 1 -C 4 -acyl group
- R 7 and R 8 are the same or different and are hydrogen, C 1 -C 4 -acyl, C 1 -C 6 -alkyl, C 2 -C 4 -alkenyl or phenyl, and
- R 9 is hydrogen, a C 1 -C 4 -acyl group, a group R 10 --O--CO, a carbamoyl group R 11 R 12 N--CO--, a sulphonyl group R 10 --SO 2 , cyano or nitro.
- R 6 is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl, with a sulphonyl chloride of general formula III ##STR5## in which R 7 , R 8 , R 9 and X have the meanings given above in a suitable solvent and in the presence of an acid acceptor, or
- R 7 and X have the meanings given above in a suitable solvent, optionally in the presence of an acid acceptor and/or catalyst, and reacting the resulting compound of general formula VI ##STR7## in which Ar, R 7 , R 9 and X have the meanings given above and R 6 is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl, with an ortho ester of general formula VII
- R 10 has the meaning given above, except hydrogen
- R 8 is hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo and/or C 1 -C 4 -alkoxy, a phenyl-C 1 -C 6 -alkyl, phenyl-C 2 -C 6 -alkenyl or phenyl-C 2 -C 6 -alkynyl group, each of which is optionally substituted by halo, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or halo-C 1 -C 4 -alkyl, or phenyl, substituted by R 1 , R 2 , R 3 , R 4 and R 5 , in a suitable solvent
- R 7 and X have the meanings given above in a suitable solvent, optionally in the presence of an acid acceptor and/or catalyst, or
- R 10 has the meaning given above, except hydrogen and Hal is chlorine or bromine, or of general formula XII
- M is a single equivalent of a metal
- Y is hydrogen, hydroxy, lower alkyl, lower alkoxy or an amino group, in a suitable solvent.
- reaction variants are preferably carried out in the presence of a diluent.
- a diluent there are used solvents which are inert to the reactants.
- solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, that can optionally be chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol and ethylene glycol, esters,
- the reaction is suitably carried out between room temperature and the boiling point of the particular reaction mixture.
- the reaction can be carried out under atmospheric pressure but if desired higher or lower pressures can be used.
- Process variant A is preferably carried out in chlorinated hydrocarbons, such as dichloromethane or dichloroethane, in the presence of a catalyst and and/or acid acceptor.
- chlorinated hydrocarbons such as dichloromethane or dichloroethane
- a catalyst and and/or acid acceptor examples of these are tertiary amines such as for example triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridine and pyridine.
- tertiary amines such as for example triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridine and pyridine.
- Pyridine can be used both as catalyst and as a solvent.
- Process variants B and C are preferably carried out in diluents such as, aliphatic, alicyclic and aromatic hydrocarbons, that can optionally be chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, esters, such as for example ethyl acetate and amyl acetate, amide, such
- Process variant D is preferably carried out by reacting a compound of general formula IX in a suitable solvent with a compound of general formula X, XI or XII, filtering off the salts which as general rule are highly insoluble and recovering the desired compounds after evaporation of the solvent.
- Process variant E is preferably carried out by reacting a compound of general formula XIII in a suitable solvent with a metal base, such as a metal hydroxide, metal hydride, metal alkyl or metal amide, and the salts which as a general rule are highly insoluble can be recovered by filtration or by evaporation of the solvent.
- a metal base such as a metal hydroxide, metal hydride, metal alkyl or metal amide
- the compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced poressure, by precipitation with water or by extraction.
- a higher level of purity can be achieved as a rule by column chromatography as well as by fractional distillation or crystallisation.
- the compounds of the invention are, as a rule, colorless or odourless crystals that are slightly soluble in water and in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxane, nitriles, such as acetonitrile, alcohols, such as methanol and ethanol, amides, such as dimethylformamide, and sulphoxides, such as dimethyl sulphoxide.
- aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble in halogenated hydrocarbons, such as chloroform,
- the sulphonyl chlorides of general formula III are new and can be prepared as described in the literature or by known methods by reacting a 2-benzylthio-6,7-dihydropyrazolo[1,5-a][1,3,5]triazin-7-one of general formula XV ##STR12## in which R 7 , R 8 , R 9 and X have the meanings given above, with chlorine in water or a water/acetic acid mixture.
- Amines of general formula II, isocyanates and isothiocyanates of general formula V and orthoesters of general formula VII are in the main commercially available or can be prepared by known processes or as described in the literature.
- the compounds of the invention influence plant growth and can therefore be used as plant growth regulators and especially as herbicides. Surprisingly, the compounds of the invention show a wide activity against monocotyledonous and dicotyledonous weeds with good selectivity in crops. Whether the compounds of the invention act as total or selective herbicides depends mainly on the rates of use but also on the species and the time of use.
- the compounds can be used in seed treatments, and in pre or post emergent use.
- the compounds of the invention can used for example against the following plant species:
- the compounds can be used in important agricultural crops, such as wheat, barley, rice and cotton.
- the compounds are also suitable for weed control in industrial and railway installations and also roads and verges, with or without vegetation, in forests, woodlands, berry fruit and hop installations, as well as plantations.
- the rates of use can vary over a wide range. They depend generally on the nature of the desired effects. In general the rates of use lie between 0.01 and 5 kg of active ingredient per hectare and preferably for example in weed control between 0.1 and 0.5 kg of active ingredient per hectare.
- the compounds of the invention can be used either alone or in admixture with one another or with other active agents.
- other plant-protective agents or pesticides can be added, depending on the purpose for the treatment.
- other herbicides can also be added.
- Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 34, No. 5 (1986) under the heading "Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".
- An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils.
- suitable adjuvants such as organic solvents, wetting agents and oils.
- Such additives may allow a decrease in the dose.
- Suitable mixture partners may include phospholipids, e.g. phosphatidylcholine, hydrated phosphatidylcholines phosphatidylethanolamine, N-acyl-phosphatidylethanolamines, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
- phospholipids e.g. phosphatidylcholine, hydrated phosphatidylcholines phosphatidylethanolamine, N-acyl-phosphatidylethanolamines, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
- the designated active ingredients or their mixtures can suitable be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting emulsifying and/or dispersing adjuvants.
- Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil fractions and plant oils.
- Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
- mineral earths e.g. bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
- surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.
- compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.
- the agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 l/ha.
- the agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
- compositions can be carried out in known manner, for example by milling or mixing processes.
- individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.
- Formulations can be prepared, for example, from the following ingredients.
- a solution of sodium methanolate was prepared from from 80.49 g (3.5 mol) sodium and 1050 ml methanol. 200.2 g (2.0 mol) of 99% methyl 2-cyanoacrylate was dissoved on 600 ml of this solution, the mixture cooled to 5° C. and 60 ml (1.0 mol) carbon disulphide added, dropwise, under cooling. A further 300 ml of the methanolate solution was added and the mixture cooled to 10° C. 30 ml (0.5 mol) Carbon disulphide was added dropwise, after which the remaining methanolate solution was added, and finally a further 15.75 ml (0.25 mol) carbon disulphide was added, dropwise. The mixture was stirred for 30 minutes at 15° C.
- Seeds of mono- and dicotyledenous plant species were sown in trays in humus-containing sandy soil and covered with earth.
- the compounds of the invention were applied as suspensions in 500 liters water/ha at a rate of 0.3 kg active ingredient/ha. to the soil surface before emergence of the plants.
- test pots were put in a greenhouse and the test plants cultivated under good growing conditions. Three weeks after the treatment plant damage was assessed. Untreated controls were used for comparison.
- Seeds of mono- and dicotyledenous plant species were sown in trays in humus-containing sandy soil and covered with earth.
- the compounds of the invention were applied as suspensions in 500 liters water/ha at a rate of 0.3 kg active ingredient/ha. to the soil surface after emergence of the plants.
- test pots were put in a greenhouse and the test plants cultivated under good growing conditions. Two weeks after the treatment plant damage was assessed. Untreated contols were used for comparison.
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Abstract
The invention relates to new 6,7-dihydropyrazole-[1,5-a][1,3,5]triazine-2-sulphonamides of general formula I ##STR1## in which Ar, R6, R7, R8, R9 and X have the meanings given in the description, processes for their preparation and their use as herbicides and plant growth regulants.
Description
The invention relates to new 6,7-dihydropyrazolo-[1,5-a][1,3,5]triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators.
It is known that triazolopyrimidinesulphonamides possess herbicidal activity (EP 142 152 and 150 974). However the herbicidal activity of the known compounds is not sufficient and/or selectivity problems can occur in important crops.
The object of the present invention is to make new compounds that do not show the disadvantages of the known compounds and have improved biological properties.
It has now been found that 6,7-dihydropyrazolo-[1,5-a][1,3,5]triazine-2-sulphonamides of general formula I ##STR2## in which Ar is a phenyl, naphthyl, pyridyl or thienyl group of general formula ##STR3##
R1, R2, R3, R4 and R5 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy, halo-C1 -C4 -alkyl, C1 -C4 -alkoxy, halo-C1 -C4 -alkoxy, C1 -C4 -alkylthio, C1 -C4 -alkylsulphinyl or C1 -C4 -alkylsulphonyl, halogen, C1 -C4 -alkoxy, a group R10--O--CO, a carbamoyl group R11 R12 N--CO--, an amino group R11 R12 N--, cyano, nitro, a sulphur containing group R10 --S(O)n --, an acyl group R10 --CO, a group R10 --O--CO--(CH2)n, or phenyl or phenoxy, both of which are optionally substituted by one or more of C1 -C4 -alkyl, halo or nitro,
R6 is hydrogen, an acyl group R10 --CO, a group R10 --O--CO--, C1 -C6 -alkyl, C2 -C6 -alkenyl, C2 -C6 -alkynyl, phenyl-C1 -C4 -alkyl, a carbamoyl group R11 R12 N--CO--, an alkali metal atom, a single metal equivalent of an alkaline earth or other metals or ammonium group, optionally substituted by C1 -C6 -alkyl,
R7 and R8 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by halo and/or C1 -C4 -alkoxy, a phenyl-C1 -C6 -alkyl, phenyl-C2 -C6 -alkenyl or phenyl-C2 -C6 -alkynyl group, each of which is optionally substituted by halo, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -alkoxy-C1 -C4 -alkyl or halo-C1 -C4 -alkyl, phenyl, substituted by R1, R2, R3, R4 and R5, an acyl group R10 --CO, a group R10 --O--CO, a group R10 --O--CO--(CH2)n, a carbamoyl group R11 R12 N--CO--, or a sulphonyl group R10 --SO2,
R9 is hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by halo and/or C1 -C4 -alkoxy, a phenyl-C1 -C6 -alkyl, phenyl-C2 -C6 -alkenyl or phenyl-C2 -C6 -alkynyl group, each of which is optionally substituted by halo, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -alkoxy-C1 -C4 -alkyl or halo-C1 -C4 -alkyl, phenyl, substituted by R1, R2, R3, R4 and R5, an acyl group R10 --CO, a group R10 --O--CO, a group R10 --O--CO--(CH2)n, a carbamoyl group R11 R12 N--CO--, a sulphonyl group R10 --SO2 or R10 --O--SO2, cyano or nitro
R10 is hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl, C2 -C6 -alkynyl or phenyl-C1 -C4 -alkyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1 -C4 -alkoxy, or phenyl, optionally substituted by halo, nitro or C1 -C4 -alkyl,
R11 and R12 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1 -C4 -alkoxy, or
R11 and R12 together with the adjacent nitrogen form a pyrrolidinyl, piperidino or morpholino ring,
X is oxygen or sulphur, and
n is 0, 1 or 2, show an interesting herbicidal and plant growth regulant activity.
The term "halogen" in relationship with alkyl, alkenyl, alkynyl or phenyl means that one or more hydrogen atoms are replaced by one or more halogen atoms.
The term "halogen" means fluorine, chlorine, bromine and iodine.
6,7-Dihydropyrazolo[1,5-a][1,3,5]triazine-2-sulphonamides of general formula I which show particularly good activity are those in which
Ar is a phenyl group of general formula ##STR4##
R1 and R5 are the same or different and are halogen, methyl, trifluoromethyl, nitro, methoxy or methoxycarbonyl,
R2, R3 and R4 are the same or different and are hydrogen, halogen, trifluoromethyl or a C1 -C4 -alkyl group,
R6 is hydrogen, a single equivalent of a metal or a C1 -C4 -acyl group,
R7 and R8 are the same or different and are hydrogen, C1 -C4 -acyl, C1 -C6 -alkyl, C2 -C4 -alkenyl or phenyl, and
R9 is hydrogen, a C1 -C4 -acyl group, a group R10 --O--CO, a carbamoyl group R11 R12 N--CO--, a sulphonyl group R10 --SO2, cyano or nitro.
The compounds of the invention of general formula I can be prepared for example by
(A) reacting an amine of general formula II,
Ar--NH--R.sub.6 (II)
in which Ar has the meaning given above and R6 is hydrogen, C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl, with a sulphonyl chloride of general formula III ##STR5## in which R7, R8, R9 and X have the meanings given above in a suitable solvent and in the presence of an acid acceptor, or
(B) reacting a compound of general formula IV ##STR6## in which Ar and R9 have the meaning given above and R6 is hydrogen, C1 -C6 -acyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl, with an isocyanate or isothiocyanate of formula V
R.sub.7 --NCX (V)
in which R7 and X have the meanings given above in a suitable solvent, optionally in the presence of an acid acceptor and/or catalyst, and reacting the resulting compound of general formula VI ##STR7## in which Ar, R7, R9 and X have the meanings given above and R6 is hydrogen, C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl, with an ortho ester of general formula VII
R.sub.8 --C(OR.sub.10).sub.3 (VII)
in which R10 has the meaning given above, except hydrogen, and R8 is hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by halo and/or C1 -C4 -alkoxy, a phenyl-C1 -C6 -alkyl, phenyl-C2 -C6 -alkenyl or phenyl-C2 -C6 -alkynyl group, each of which is optionally substituted by halo, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -alkoxy-C1 -C4 -alkyl or halo-C1 -C4 -alkyl, or phenyl, substituted by R1, R2, R3, R4 and R5, in a suitable solvent, which can be the orthoester itself, or
(C) reacting a compound of general formula IV ##STR8## in which Ar and R9 have the meaning given above and R6 has the meaning given under (B), with an ortho ester of general formula VII
R.sub.8 --C(OR.sub.10).sub.3 (VII)
in which R8 and R10 have the meanings given under (B), in a suitable solvent, which can be the orthoester itself, to give a compound of formula VIII ##STR9## which is reacted with an isocyanate or isothiocyanate of formula V
R.sub.7 --NCX (V)
in which R7 and X have the meanings given above in a suitable solvent, optionally in the presence of an acid acceptor and/or catalyst, or
(D) reacting a compound of general formula IX ##STR10## in which Ar, R7, R8, R9 and X have the meanings given above and R13 is hydrogen or a single equivalent of a metal, with a compound of general formula X
R.sub.10 --Hal (X)
or of general formula XI
R.sub.10 --CO--Hal (XI)
in which R10 has the meaning given above, except hydrogen and Hal is chlorine or bromine, or of general formula XII
R.sub.10 --CO--O--COR.sub.10 (XII)
in which R10 has the meaning given above, in a suitable solvent, or
(E) reacting a compound of general formula XIII ##STR11## in which Ar, R7, R8, R9 and X have the meanings given above, with a compound of general formula XIV
M--Y (XIV)
in which M is a single equivalent of a metal, and Y is hydrogen, hydroxy, lower alkyl, lower alkoxy or an amino group, in a suitable solvent.
The particular reaction variants are preferably carried out in the presence of a diluent. For this purpose there are used solvents which are inert to the reactants.
Examples of such solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, that can optionally be chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol and ethylene glycol, esters, such as for example ethyl acetate and amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, sulphones and sulphoxides, such as for example dimethyl sulphoxide and and sulpholane, and bases, such as for example pyridine.
The reaction is suitably carried out between room temperature and the boiling point of the particular reaction mixture. The reaction can be carried out under atmospheric pressure but if desired higher or lower pressures can be used.
Process variant A is preferably carried out in chlorinated hydrocarbons, such as dichloromethane or dichloroethane, in the presence of a catalyst and and/or acid acceptor. Examples of these are tertiary amines such as for example triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridine and pyridine. Pyridine can be used both as catalyst and as a solvent.
Process variants B and C are preferably carried out in diluents such as, aliphatic, alicyclic and aromatic hydrocarbons, that can optionally be chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, esters, such as for example ethyl acetate and amyl acetate, amide, such as for example dimethylformamide and dimethylacetamide, sulphones and sulphoxides, such as for example dimethyl sulphoxide and and sulpholane, and bases, such as for example pyridine, and optionally in the presence of a catalyst and and/or acid acceptor. Examples of these are tertiary amines such as for example triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridine and pyridine.
Process variant D is preferably carried out by reacting a compound of general formula IX in a suitable solvent with a compound of general formula X, XI or XII, filtering off the salts which as general rule are highly insoluble and recovering the desired compounds after evaporation of the solvent.
Process variant E is preferably carried out by reacting a compound of general formula XIII in a suitable solvent with a metal base, such as a metal hydroxide, metal hydride, metal alkyl or metal amide, and the salts which as a general rule are highly insoluble can be recovered by filtration or by evaporation of the solvent.
The compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced poressure, by precipitation with water or by extraction.
A higher level of purity can be achieved as a rule by column chromatography as well as by fractional distillation or crystallisation.
The compounds of the invention are, as a rule, colorless or odourless crystals that are slightly soluble in water and in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxane, nitriles, such as acetonitrile, alcohols, such as methanol and ethanol, amides, such as dimethylformamide, and sulphoxides, such as dimethyl sulphoxide.
The sulphonyl chlorides of general formula III are new and can be prepared as described in the literature or by known methods by reacting a 2-benzylthio-6,7-dihydropyrazolo[1,5-a][1,3,5]triazin-7-one of general formula XV ##STR12## in which R7, R8, R9 and X have the meanings given above, with chlorine in water or a water/acetic acid mixture.
Amines of general formula II, isocyanates and isothiocyanates of general formula V and orthoesters of general formula VII are in the main commercially available or can be prepared by known processes or as described in the literature.
The compounds of the invention influence plant growth and can therefore be used as plant growth regulators and especially as herbicides. Surprisingly, the compounds of the invention show a wide activity against monocotyledonous and dicotyledonous weeds with good selectivity in crops. Whether the compounds of the invention act as total or selective herbicides depends mainly on the rates of use but also on the species and the time of use.
The compounds can be used in seed treatments, and in pre or post emergent use.
The compounds of the invention can used for example against the following plant species:
Dicotyledonous weeds of the species Polygonum, Sinapis, Atriplex, Spergula, Stellaria, Galium, Viola, Cirsium, Amaranthus, Ipomoea, Xanthium, Abutilon, Chenopodium, Cassia, convolvulus, Mentha, Veronica, Matricaria, Solanum, Lamium, Thlapsi, Capsella, Datura, Galinsoga, Mercurialis, Rhaphanus, Vicia, Portulaca, Physalis, Sida, Anoda, Euphorbia, Myosotis, Centaurea, Brassica, Chrysanthemum and Helianthus;
Monocotyledonous weeds of the species Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Apera, Rottoboellia, Triticum and Hordeum.
The compounds can be used in important agricultural crops, such as wheat, barley, rice and cotton.
The use of the compounds of the invention is not limited to the weeds and crops mentioned above but can also be applied in a similar way to other plants.
The compounds are also suitable for weed control in industrial and railway installations and also roads and verges, with or without vegetation, in forests, woodlands, berry fruit and hop installations, as well as plantations.
The rates of use can vary over a wide range. They depend generally on the nature of the desired effects. In general the rates of use lie between 0.01 and 5 kg of active ingredient per hectare and preferably for example in weed control between 0.1 and 0.5 kg of active ingredient per hectare.
The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for the treatment. When it is desired to broaden the spectrum of activity, other herbicides can also be added. Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 34, No. 5 (1986) under the heading "Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".
An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.
Suitable mixture partners may include phospholipids, e.g. phosphatidylcholine, hydrated phosphatidylcholines phosphatidylethanolamine, N-acyl-phosphatidylethanolamines, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
The designated active ingredients or their mixtures can suitable be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting emulsifying and/or dispersing adjuvants.
Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil fractions and plant oils.
Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.
The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.
The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 l/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.
Formulations can be prepared, for example, from the following ingredients.
(A) Wettable Powder
(1) 25 percent by weight active ingredient
60 percent by weight kaolin
10 percent by weight silicic acid
5 percent by weight of a mixture of calcium lignosulphonate and the sodium salt of N-methyl-N-oleyltaurine
(2) 40 percent by weight active ingredient
25 percent by weight bentonite
25 percent by weight colloidal silicic acid
10 percent by weight of a mixture of calcium lignosulphonate and alkylphenyl polyglycol ether
(B) Paste
45 percent by weight active ingredient
5 percent by weight sodium aluminium silicate
15 percent by weight cetyl polyglycol ether with 8 mol of ethylene oxide
2 percent by weight spindle oil
10 percent by weight polyethylene glycol
23 percent by weight water
(C) Emulsifiable Concentrate
25 percent by weight active ingredient
15 percent by weight cyclohexanone
55 percent by weight xylene
5 percent by weight of a mixture of calcium dodecylbenzenesulphonate and nonylphenolpolyoxyethylene.
The following examples illustrate the preparation of compound according to the invention.
2.84 g (17.5 mmol) 2,6-Dichloroaniline was stirred in 15 ml pyridine with 5.00 g (15.6 mmol) 6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo[1,5-a][1,3,5]-triazine-2-sulphonyl chloride for 15 hours at 50° C. and the undissolved residue filtered. The filtrate was concentrated, the residue treated with 2N sulphuric acid, the product suction filtered, chromatographed with hexane/ethyl acetate over silica gel and recrystallised from ethyl acetate.
Yield: 1.97 g=28% of theory.
M.p.: 265°-267° C.
Elementary analysis
Calc. (%): C 40.37 H 2.94 N 15.69 S 7.19 Cl 15.89. Found (%): C 40.45 H 3.34 N 14.94 S 7.21 Cl 15.70.
15.50 g (43 mmol) 2-Benzylthio-6,7-dihydro-3-methoxycarbonyl-5,6-dimethyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-7-thione was suspended in 200 ml water/acetic acid (1:1 mixture). At 10° C., chlorine was introduced over 3 hours. The product was extracted with methylene chloride and dried over magnesium sulphate. After concentrating, the residue was treated with ether and the product suction filtered.
Yield: 9.70 g=70% of theory.
M.p.: 188°-190° C.
6.77 g (20.1 mmol) 5-Amino-B 3-benzylthio-4-methoxycarbonyl-N-methylpyrazole-1-carbothioamide was stirred in 35 ml triethyl orthoacetate allowing the ethanol which formed to distil off. After cooling, the product was suction filtered, washed with ether and dried.
Yield: 5.35 g=74% of theory.
M.p.: 212°-213° C.
Elementary analysis Calc. (%): C 53.51 H 4.47 N 15.54 S 17.79. Found (%): C 53.37 H 4.27 N 15.56 S 18.11.
45.11 g (0.127 mol) Methyl 3,3-dibenzylthio-2-cyanoacrylate and 13.35 g (0.127 mol) 4-methylthiosemicarbazide in 225 ml ethanol were heated under reflux for 10 hours. After cooling, the product was suction filtered, washed with ether and dried.
Yield: 33.61 g=79% of theory.
M.p.: 162°-163° C.
Elementary analysis Calc. (%): C 49.98 H 4.79 N 16.65 S 19.06. Found (%): C 50.00 H 5.12 N 16.78 S 19.48.
A solution of sodium methanolate was prepared from from 80.49 g (3.5 mol) sodium and 1050 ml methanol. 200.2 g (2.0 mol) of 99% methyl 2-cyanoacrylate was dissoved on 600 ml of this solution, the mixture cooled to 5° C. and 60 ml (1.0 mol) carbon disulphide added, dropwise, under cooling. A further 300 ml of the methanolate solution was added and the mixture cooled to 10° C. 30 ml (0.5 mol) Carbon disulphide was added dropwise, after which the remaining methanolate solution was added, and finally a further 15.75 ml (0.25 mol) carbon disulphide was added, dropwise. The mixture was stirred for 30 minutes at 15° C. 598.68 g (3.5 mol) Benzyl bromide was added dropwise, with cooling. The mixture was stirred for 2 hours at 20° C., the solvent distilled and the residue treated with ice-water. The product was suction filtered, washed with water and ether and dried.
Yield: 521.2 g=84% of theory.
M.p.: 100°-101° C.
Elementary analysis Calc. (%): C 64.19 H 4.82 N 3.94 S 18.04. Found (%): C 64.14 H 4.82 N 4.18 S 17.82.
2.6 g (6.7 mmol) N-(2,6-difluorophenyl)-4-methoxycarbonyl-5-(1-methoxyethylidenamino)pyrazole-3-sulphonamide was stirred with 20 ml tetrahydrofuran, 0.88 ml (12 mmol) methyl isothiocyanate and 0.71 ml (7 mmol) triethylamine for 8 hours at 50° C. The mixture was cooled to 5° C., the crystals suction filtered and washed with tetrahydrofuran and ether.
Yield: 1.5 g=52% of theory.
M.p.: 284°-286° C.
Elementary analysis Calc. (%): C 41.95 H 3.05 N 16.31 S 14.93 F 8.85. Found (%): C 41.89 H 3.49 N 16.23 S 15.09 F 8.91.
5.0 g (15mmol) 5-amino-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamide was heated under reflux with 50 ml acetonitrile, 2.1 ml (17.5 mmol) triethyl orthoacetate and 3 drops acetic acid for 8 hours. The undissolved residue was filtered and the filtrate concentrated. The residue was chromatographed with hexane/ethyl acetate over silica gel and recrystallised from ether.
Yield: 4.8 g=82% of theory.
M.p.: 194°-196° C.
Elementary analysis Calc. (%): C 43.30 H 3.63 N 14.43 S 8.26 F 9.78. Found (%): C 43.27 H 3.98 N 14.13 S 8.09 F 9.69.
7.50 g (20 mmol) 5-acetamido-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamide was suspended in 80 ml 4.4N methanolic hydrochloric acid and heated under reflux for 5 hours. The solvent was distilled and the residue treated with water. The product was suction filtered, washed with water and dried.
Yield: 6.2 g=93% of theory.
M.p.: 265°-266° C.
Elementary analysis Calc. (%): C 39.76 H 3.03 N 16.86 S 9.65 F 11.44. Found (%): C 40.23 H 3.25 N 17.12 S 9.80 F 11.46.
23.63 g (177.5 mmol) of 97% 2,6-difluoroaniline and 1.48 g N,N-dimethyl-4-aminopyridine was dissolved in 225 ml pyridine and 25.0 g (88.75 mmol) 5-acetamido-4-methoxycarbonylpyrazole-3-sulphonyl chloride added portionwise. The mixture was stirred for 48 hours at 25° C. The pyridine was distilled and the residue dissolved in 510 ml methylene chloride washed twice with 370 ml 5N hydrochloric acid and twice with 370 ml water, dried over magnesium sulphate and concentrated. The residue was triturated with ether, the product suction filtered, washed with ether and dried.
Yield: 17.53 g=53% of theory.
M.p.: 221°-222° C.
Elementary analysis Calc. (%): C 41.71 H 3.23 N 14.97 S 8.57 F 10.15. Found (%): C 41.66 H 3.30 N 14.83 S 8.54 F 10.23.
73.0 g (239 mmol) Methyl 5-acetamido-3-benzylthiopyrazole-4-carboxylate was dissolved in 470 ml methylene chloride and treated with 124.15 g silica gel and 25.6 g water and cooled to 0° C. 160.6 g (1.19 mol) Sulphuryl chloride in 730 ml methylene chloride was added dropwise. The mixture was stirred for 3 hours at 0° C., filtered, washed several times with methylene chloride, dried over magnesium sulphate and concentrated. The residue was triturated with ether/hexane, the crystals suction filtered, washed with hexane and dried.
Yield: 51.9 g=77% of theory.
M.p.: 143°-144° C.
Elementary analysis Calc. (%): C 29.85 H 2.86 N 14.92 S 11.38 F 12.59. Found (%): C 29.92 H 2.76 N 14.87 S 11.40 F 12.51.
70.5 g (0.27 mol) Methyl 5-amino-3-benzylthiopyrazole-4-carboxylate was dissolved at 80° C. in 135 ml glacial acetic acid and treated with 27.75 g (0.27 mol) acetic anhydride. The solution was heated under reflux for 7 hours and concentrated. The residue was recrystallised from ether, the crystals suction filtered, washed with ether and dried.
Yield: 73.2 g=89% theory.
M.p.: 136°-137° C.
Elementary analysis Calc. (%): C 55.07 H 4.95 N 13.76 S 10.50. Found (%): C 55.17 H 4.77 N 13.80 S 10.79.
124.34 g (0.35 mol) Methyl 3,3-dibenzylthio-2-cyanoacrylate and 46.70 g (0.35 mol) t-butyl hydrazinoformate was heated under reflux for 3.5 hours in 700 ml ethanol and concentrated. The residue was treated with 700 ml glacial acetic acid and stirred for 3 hours at 110° C. and for 1 hour at 5° C. The product was suction filtered, washed with glacial acetic acid and hexane and dried.
Yield: 70.9 g=77% of theory.
M.p.: 111°-112° C.
Elementary analysis Calc. (%): C 54.73 H 4.97 N 15.96. Found (%): C 54.02 H 4.68 N 15.93.
1.5 g (3.9 mmol) N-(2,6-difluorophenyl)-4-methoxycarbonyl-5-(1-methoxyethylidenamino)pyrazole-3-sulphonamide was stirred with 20 ml tetrahydrofuran, 0.29 g (5.0 mmol) methyl isocyanate and 0.39 ml (3.9 mmol) triethylamine for 48 hours at 25° C. The crystals were suction filtered and washed with tetrahydrofuran and ether.
Yield: 1.3 g=81% of theory.
M.p.: 257°-259° C.
Elementary analysis Calc. (%): C 43.58 H 3.17 N 16.94 S 7.76 F 9.19. Found (%): C 43.34 H 3.23 N 16.80 s 7.53 F 9.03.
In a similar manner to Examples 1 to 3 the following compounds of the invention were prepared were prepared.
______________________________________
Ex-
am-
ple Physical
No Name of Compound Constant
______________________________________
4 N--(2,6-Dichlorophenyl)-6,7-dihydro-
mp:304-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
305° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
5 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:262-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
264° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
6 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:312-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
314° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
7 N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-
mp:240-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
242° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
8 N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-
mp:285-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
286° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
9 N--(2-Chloro-6-methylphenyl)-6,7-dihydro-
mp:259-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
261° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
10 N--(2-Chloro-6-methylphenyl)-6,7-dihydro-
mp:295-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
297° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
11 N--(2,6-Dibromophenyl)-6,7-dihydro-
mp:293-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
295° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
12 N--(2,6-Dibromophenyl)-6,7-dihydro-
mp:327-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
330° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
13 N--(2-Methyl-6-nitrophenyl)-6,7-dihydro-
mp:230-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
232° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide.
hydrate
14 N--(2-Methyl-6-nitrophenyl)-6,7-dihydro-
mp:271-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
274° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
15 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
mp:210-
N--(2-methoxycarbonyl-6-methylphenyl)-7-thiox-
212° C.
o-pyrazol[1,5-a][1,3,5]triazine-2-sulphonamide
16 N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-
mp:276-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
278° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide,
x hydrate
17 N--(2,6-Dichlorophenyl)-6,7-dihydro-
mp:283-
5,6-dimethyl-3-ethoxycarbonyl-7-oxo-
284° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
18 N--(2,6-Difluorophenyl)-6,7-dihydro-
mp:221-
5,6-dimethyl-3-ethoxycarbonyl-7-oxo-
223° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
19 N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-
mp:214-
5,6-dimethyl-3 ethoxycarbonyl-7-oxo-
217° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
20 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:228-
5,6-dimethyl-3-ethoxycarbonyl-7-oxo-
230° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
21 N--(2,6-Dibromophenyl)-6,7-dihydro-
mp:295-
5,6-dimethyl-3-ethoxycarbonyl-7-oxo-
297° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
22 N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-
mp:285-
5,6-dimethyl-3-ethoxycarbonyl-7-oxo-
286° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
23 N--(2,6-Dichlorophenyl)-6,7-dihydro-
mp:272-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
274° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
24 6,7-Dihydro-5,6-dimethyl-3-ethoxycarbonyl-
mp:182-
N--(2-methoxycarbonyl-6-methyphenyl)-7-thioxo-
186° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
25 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:257-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
259° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
26 N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-
mp:232-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
235° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
27 N--(2,6-Difluorophenyl)-6,7-dihydro-
mp:214-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
216° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
28 N--(2-Chloro-6-methylphenyl)-6,7-dihydro-
mp:225-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
226° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
29 N--(2,6-Dibromophenyl)-6,7-dihydro-
mp:285-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
287° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
30 N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-
mp:291-
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
293° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
31 3-Cyano-N--(2,6-dichlorophenyl)-6,7-dihydro-
mp:338-
5,6-dimethyl-7-oxopyrazolo-
341° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
32 3-Cyano-N--(2,6-dibromophenyl)-6,7-dihydro-
mp:
5,6-dimethyl-7-oxopyrazolo-
303 (dec)
[1,5-a][1,3,5]triazine-2-sulphonamide
33 3-Cyano-N--(2,6-dichloro-3-methylphenyl)-
mp:298-
6,7-dihydro-5,6-dimethyl-7-oxopyrazolo
303° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
34 3-Cyano-6,7-dihydro-5,6-dimethyl-
mp:258-
N--(2-methoxycarbonyl-6-methylphenyl)-7-oxo-
262° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
35 3-Cyano-N--(2,6-dichlorophenyl)-6,7-dihydro-
mp:279-
5,6-dimethyl-7-thioxopyrazolo-
282° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
36 3-Cyano-N--(2,6-dichloro-3-methylphenyl)-
mp:272-
6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-
273° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
37 3-Cyano-N--(2,6-dibromophenyl)-6,7-dihydro-
mp:300°
5,6-dimethyl-7-thioxopyrazolo-
C. (dec)
[1,5-a][1,3,5]triazine-2-sulphonamide
38 3-Cyano-6,7-dihydro-5,6-dimethyl-
mp:248-
N--(2-methoxycarbonyl-6-methylphenyl)-7-thioxo-
249° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
39 3-Carbamoyl-N--(2,6-dichlorophenyl)-
mp:303-
6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-
305° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
40 3-Carbamoyl-N--(2,6-dichloro-3-methylphenyl)-
mp:307°
6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-
C. (dec)
[1,5-a][1,3,5]triazine-2-sulphonamide
41 3-Carbamoyl-N--(2,6-dibromophenyl)-
mp:274-
6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-
275° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
42 3-Carbamoyl-N--(2,6-dichlorophenyl)-
mp:295-
6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-
296° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
43 3-Carbamoyl-N--(2,6-dichloro-3-methylphenyl)-
mp:269°
6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-
C. (dec)
[1,5-a][1,3,5]triazine-2-sulphonamide
44 3-Carbamoyl-N--(2,6-dibromophenyl)-
mp:279-
6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-
280° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
45 N--(2,6-Dichlorophenyl)-6,7-dihydro-
mp:289-
5,6-dimethyl-3-methylsulphonyl-7-oxopyrazolo-
292° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
46 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:273-
5,6-dimethyl-3-methylsulphonyl-7-oxopyrazolo-
275° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
47 N--(2,6-Dichlorophenyl)-6,7-dihydro-
mp:318-
5,6-dimethyl-3-methylsulphonyl-7-thioxo-
320° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
48 N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-
mp:290-
5,6-dimethyl-3-methylsulphonyl-7-thioxo-
293° C.
pyrazolo[ 1,5-a][1,3,5]triazine-2-sulphonamide
49 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
N--(2-methoxycarbonyl-6-methylphenyl)-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
50 N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
51 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
7-oxo-N--(2-trifluoromethylphenyl)-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
52 6,7-Dihydro-5,6-dimethyl-N--(5,6-dimethyl-
2-nitrophenyl)-3-methoxycarbonyl-7-oxo
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
53 N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
54 N--(2-Bromo-6-chloro-3-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-
oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
55 N--(2-Bromo-6-chloro-5-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-
oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
56 N--(2,6-Dibromo-3-methylphenyl)-6,7-dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
57 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl
N--(6-methyl-2-trifluoromethylphenyl)-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
58 N--(2-Difluoromethoxy-6-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-
oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
59 6,7-Dihydro-5,6-dimethyl-N--(3,6-dimethyl-
2-nitrophenyl)-3-methoxycarbonyl-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
60 N--[2,6-Bis(difluoromethoxyphenyl)]6-Bis(difluoromethoxyphenyl)]-6,7-
dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
61 6,7-Dihydro-5,6-dimethyl-N--(6-fluoro-
2-methoxycarbonyl-3-methylphenyl)-3-methoxy-
carbonyl-7-oxo-pyrazolo[1,5-a][1,3,5]triazine-
2-sulphonamide
62 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
N--(2-methoxy-6-trifluoromethylphenyl)-7-oxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
63 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
7-thioxo-N--(2-trifluoromethylphenyl)-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
64 6,7-Dihydro-5,6-dimethyl-N--(5,6-dimethyl-
2-nitrophenyl)-3-methoxycarbonyl-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
65 N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
66 N--(2-Bromo-6-chloro-3-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-
7-thioxopyrazolo[1,5-a][1,3,5]triazine-
2-sulphonamide
67 N--(2-Bromo-6-chloro-5-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-
7-thioxopyrazolo[1,5-a][1,3,5]triazine
2-sulphonamide
68 N--(2-Dibromo-3-methylphenyl)-6,7-dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
69 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
N--(6-methyl-2-trifluoromethylphenyl)-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
70 N--(2-Difluoromethoxy-6-methylphenyl)-
6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-
7-thioxopyrazolo[1,5-a][1,3,5]triazine-2-
sulphonamide
71 6,7-Dihydro-5,6-dimethyl-N--(3,6-dimethyl-
2-nitrophenyl)-3-methoxycarbonyl-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2 sulphonamide
72 N--[2,6-Bis(difluoromethoxyphenyl)]6-Bis(difluoromethoxyphenyl)]-6,7-
dihydro-
5,6-dimethyl-3-methoxycarbonyl-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
73 6,7-Dihydro-5,6-dimethyl-N--(6-fluoro-
2-methoxycarbonyl-3-methylphenyl)-3-methoxy-
carbonyl-7-thioxopyrazolo[1,5-a][1,3,5]triazine
2-sulphonamide
74 6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-
N--(2-methoxy-6-trifluoromethylphenyl)-7-thioxo-
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
75 N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-
mp:
5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-
210° C.
pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide
76 3-Carbamoyl-N--(2-carboxy-6-methylphenyl)
mp:257-
6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-
258° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
77 3-Carbamoyl-N--(2-carboxy-6-methylphenyl)-
mp:267-
6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-
268° C.
[1,5-a][1,3,5]triazine-2-sulphonamide
______________________________________
The following examples illustrate the posibilties for areas of use of the compounds of the invention.
Seeds of mono- and dicotyledenous plant species were sown in trays in humus-containing sandy soil and covered with earth. The compounds of the invention were applied as suspensions in 500 liters water/ha at a rate of 0.3 kg active ingredient/ha. to the soil surface before emergence of the plants.
After the treatment the test pots were put in a greenhouse and the test plants cultivated under good growing conditions. Three weeks after the treatment plant damage was assessed. Untreated controls were used for comparison.
As the table clearly shows numerous plant species weeds were destroyed or damaged. Wheat and barley were ressistant to the treatment.
In the following table:
__________________________________________________________________________
Compounds of
invention
Tr
Ho
Br He
St Ab
Ma Vi
Ch So
Ec Se Ga
__________________________________________________________________________
Example 1
0 0 3 3 2 3 4 4 4 3 3 3 3
Example 2
2 2 3 3 2 2 4 3 3 4 4 3 3
Example 3
0 0 3 3 1 2 4 3 3 3 3 4 2
Example 4
1 0 3 3 3 3 4 3 3 3 3 4 4
Example 5
0 0 3 3 3 3 4 3 4 2 2 2 3
Example 6
0 1 2 3 3 2 4 4 4 3 3 2 4
Example 7
0 1 2 3 2 2 4 3 3 2 2 2 2
Example 8
1 2 3 3 2 2 4 3 4 4 3 4 3
Example 9
0 1 2 3 2 2 4 3 3 3 2 3 3
Example 10
1 1 3 3 3 2 4 3 3 3 3 2 3
Example 15
0 --
1 1 -- 0 4 0 -- --
-- 0 0
Example 16
1 --
1 2 -- 0 4 --
-- --
-- 1 2
Example 17
0 --
3 3 -- 3 4 --
-- --
-- 3 3
Example 18
0 --
3 3 -- 3 3 --
-- --
-- 2 2
Example 19
0 --
3 3 -- 3 4 --
-- --
-- 2 2
Example 20
0 --
3 2 -- 1 4 --
-- --
-- 0 2
Example 21
1 --
3 2 -- 1 4 --
-- --
-- 3 3
Example 22
0 --
-- --
-- 3 4 --
-- --
-- 4 4
Example 23
0 --
3 3 -- 3 4 --
-- --
-- 3 3
Example 24
0 --
0 0 -- 0 3 1 -- --
-- 0 0
Example 25
0 --
3 3 -- 2 4 --
-- --
-- 2 4
Example 26
0 --
3 2 -- 2 4 --
-- --
-- 0 2
Example 27
1 --
2 2 -- 1 4 --
-- --
-- 0 2
Example 28
0 --
2 1 -- 0 3 --
-- --
-- 0 3
Example 29
1 --
3 2 -- 0 4 --
-- --
-- 0 3
Example 30
0 --
-- --
-- 3 4 --
-- --
-- 4 4
Example 39
0 --
3 3 -- 0 4 --
-- --
-- 3 3
Example 42
1 --
3 3 -- 0 4 --
-- --
-- 3 3
Example 45
0 --
-- --
-- 0 2 --
-- --
-- 1 2
Example 46
0 --
-- --
-- 2 4 --
-- --
-- 2 3
Example 47
0 --
-- --
-- 0 3 --
-- --
-- 0 2
Example 48
0 --
-- --
-- 1 4 --
-- --
-- 2 4
Control 0 0 0 0 0 0 0 0 0 0 0 0 0
__________________________________________________________________________
0 = no activity
4 total destruction of the plant.
Tr = Triticum aestivum
Ho = Hordeum distichum
Br = Brassica napus napus
He = Helianthus annuus
St = Stellaria media.
Ab = Abutilon hybridum
Ma = Matricaria chamomilla
Vi = Viola tricolor
Ch = Chrysanthemum segetum
So = Sorghum sativum
Ec = Echinochloa crusgalli
Se = Setaria italica
Ga = Galium aparine
-- = not tested
Seeds of mono- and dicotyledenous plant species were sown in trays in humus-containing sandy soil and covered with earth. The compounds of the invention were applied as suspensions in 500 liters water/ha at a rate of 0.3 kg active ingredient/ha. to the soil surface after emergence of the plants.
After the treatment the test pots were put in a greenhouse and the test plants cultivated under good growing conditions. Two weeks after the treatment plant damage was assessed. Untreated contols were used for comparison.
As the table clearly shows numerous plant species weeds were destroyed or damaged. Wheat and barley were ressistant to the treatment.
In the following table:
______________________________________
Compounds
of
invention Tr Ho Br Ly Me He St Ab Ma Vi Ch Ga
______________________________________
Example 1
0 0 3 4 3 3 4 2 3 2 3
4
Example 2 1 0 3 3 3 3 4 2 3 3 3 3
Example 3 0 0 3 3 4 3 3 2 2 3 2 3
Example 4 1 2 4 4 3 4 4 2 3 1 4 4
Example 5 0 0 2 3 3 3 2 2 3 3 4 3
Example 6 0 0 3 4 3 4 3 2 4 2 4 4
Example 7 0 0 3 3 3 3 2 3 2 2 2 3
Example 8 0 2 3 3 3 3 4 3 3 2 4 4
Example 9 0 0 2 2 2 2 3 1 2 1 2 3
Example 10 0 0 2 3 2 3 3 2 2 2 3 3
Control 0 0 0 0 0 0 0 0 0 0 0 0
______________________________________
0 = no activity
4 total destruction of the plant.
Tr = Triticum aestivum
Ho = Hordeum distichum
Br = Brassica napus napus
Ly = Lycopersicon esculentum
Me = Medicago sativa
He = Helianthus annuus
St = Stellaria media.
Ab = AbutiIon hybridum
Ma = Matricaria chamomilla
Vi = Viola tricolor
Ch = Chrysanthemum segetum
Ga = Galium aparine
Claims (16)
1. 6,7-Dihydropyrazole[1,5-a][1,3,5]triazine-2-sulphonamides of formula I ##STR13## in which Ar is phenyl, naphthyl, pyridyl or thienyl group of general formula ##STR14## R1, R2, R3, R4 and R5 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy, halo-C1 -C4 -alkyl, C1 -C4 -alkoxy, halo-C1 -C4 -alkoxy, C1 -C4 -alkylthio, C1 -C4 -alkylsulphinyl or C1 -C4 -alkylsulphonyl, halogen, C1 -C4 -alkoxy, a group R10 --O--CO, a carbamoyl group R11 R12 N--CO--, an amino group R11 R12 N--, cyano, nitro, a sulphur containing group R10 --S(O)n --, an acyl group R10 --CO, a group R10 --O--CO--(CH2)n, or phenyl or phenoxy, both of which are optionally substituted by one of more of C1 -C4 -alkyl, halo or nitro,
R6 is hydrogen, an acyl group R10 --CO, a group R10 --O--CO--, C1 -C6 -alkyl, C2 -C6 -alkenyl, C2 -C6 -alkynyl, phenyl-C1 -C4 -alkyl, a carbamoyl group R11 R12 N--CO--, an alkali metal, an alkaline earth metal or ammonium group, optionally substituted by C1 -C6 -alkyl,
R7 and R8 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by halo or C1 -C4 -alkoxy, a phenyl-C1 -C6 -alkyl, phenyl-C2 -C6 -alkenyl or phenyl-C2 -C6 -alkynyl group, each of which is optionally substituted by halo, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -alkoxy-C1 -C4 -alkyl or halo-C1 -C4 -alkyl, phenyl, substituted by R1, R2, R3, R4 and R5, an acyl group R10 --CO, a group R10 --O--CO, a group R10 --O--CO--(CH2)n, a carbamoyl group R11 R12 N--CO--, or a sulphonyl group R10 --SO2,
R9 is hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by halo or C1 -C4 -alkoxy, a phenyl-C1 -C6 -alkyl, phenyl-C2 -C6 -alkenyl or phenyl-C2 -C6 -alkynyl group, each of which is optionally substituted by halo, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -alkoxy-C1 -C4 -alkyl or halo-C1 -C4 -alkyl, phenyl, substituted by R1, R2, R3, R4 and R5, an acyl group R10 --CO, a group R10 --O--CO, a group R10 --O--CO--(CH2)n, a carbamoyl group R11 R12 N--CO--, a sulphonyl group R10 --SO2 or R10 --O--SO2, cyano or nitro
R10 is hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl, C2 -C6 -alkynyl or phenyl-C1 -C4 -alkyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1 -C4 -alkoxy, or phenyl, optionally substituted by halo, nitro or C1 -C4 -alkyl,
R11 and R12 are the same or different and are hydrogen, a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1 -C4 -alkoxy, or
R11 and R12 together with the adjacent nitrogen form a pyrrolidinyl, piperidino or morpholino ring,
X is oxygen or sulphur, and
n is 0, 1 or 2.
2. 6,7-Dihydropyrazole[1,5-a][1,3,5]triazine-2-sulphonamides according to claim 1, in which Ar is a phenyl group of general formula ##STR15## R1 and R5 are the same or different and are halogen, methyl, trifluoromethyl, nitro, methoxy or methoxycarbonyl,
R2, R3 and R4 are the same or different and are hydrogen, halogen, trifluoromethyl or a C1 -C4 -alkyl group,
R6 is hydrogen, said metal or a C1 -C4 -acyl group,
R7 and R8 are the same or different and are hydrogen, C1 -C4 -acyl, C1 -C6 -alkyl, C2 -C4 -alkenyl or phenyl, and
R9 is hydrogen, a C1 -C4 -acyl group, a group R10 --O--CO, a carbamoyl group R11 R12 N--CO--, a sulphonyl group R10 --SO2, cyano or nitro.
3. A herbicidal and plant-growth regulant composition with comprises an effective herbicidal and plant growth regulant amount of a compound according to claim 1, in admixture with carriers and diluents.
4. A method of combating weeds which comprises applying to the weeds or their locus an effective herbicidal amount of a compound according to claim 1.
5. A method of regulating the growth of plants which comprises applying to the plants or their locus a plant growth regulant amount of a compound according to claim 1.
6. A herbicidal and plant-growth regulant composition which comprises a compound according to claim 2, in admixture with carriers and diluents.
7. A method of combating weeds which comprises applying to the weeds or their locus a compound according to claim 2.
8. A method of regulating the growth of plants which comprises applying to the plants or their locus a plant growth regulant amount of a compound according to claim 2.
9. N-(2,6-disubstituted phenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-pyrazolo[1,5-a][1,3,5]triazine-2-sulfonamide according to claim 2, in which the substituents are individually selected from the group consisting of halogen, methyl, nitro and methoxy.
10. N-(2,6-disubstituted phenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-pyrazolo[1,5-a][1,3,5]triazine-2-sulfonamide according to claim 9 in which said substituents are individually selected from the group consisting of chloro, fluoro and methyl and X is S.
11. A method of regulating the growth of plants which comprises applying to the plants or their locus a plant growth regulant amount of a compound according to claim 9.
12. A method of regulating the growth of plants which comprises applying to the plants or their locus a plant growth regulant amount of a compound according to claim 10.
13. A method of combatting weeds which comprises applying to the weeds or their locus an effective herbicidal amount of a compound according to claim 9.
14. A method of combatting weeds which comprises applying to the weeds or their locus an effective herbicidal amount of a compound according to claim 10.
15. A herbicidal and plant-growth regulant composition which comprises an effective herbicidal and plant growth regulant amount of a compound according to claim 9, in admixture with carriers and diluents.
16. A herbicidal and plant-growth regulant composition which comprises a compound according to claim 10 in admixture with carriers and diluents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873722072 DE3722072A1 (en) | 1987-07-01 | 1987-07-01 | 6,7-DIHYDRO-PYRAZOLO (1,5-A) (1,3,5) TRIAZINE-2-SULPHONIC ACID AMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDES AND PLANT GROWTH REGULATING EFFECT |
| DE3722072 | 1987-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4892576A true US4892576A (en) | 1990-01-09 |
Family
ID=6330887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/213,905 Expired - Fee Related US4892576A (en) | 1987-07-01 | 1988-06-30 | 6,7-dihydro-pyrazolo (1,5-A)(1,3,5)triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4892576A (en) |
| EP (1) | EP0297490A1 (en) |
| JP (1) | JPS6470489A (en) |
| KR (1) | KR890002154A (en) |
| CN (1) | CN1030419A (en) |
| AU (1) | AU606697B2 (en) |
| BR (1) | BR8803293A (en) |
| DD (1) | DD285921A5 (en) |
| DE (1) | DE3722072A1 (en) |
| DK (1) | DK368088A (en) |
| FI (1) | FI883168A7 (en) |
| HU (1) | HUT47393A (en) |
| IL (1) | IL86901A0 (en) |
| SU (1) | SU1616507A3 (en) |
| ZA (1) | ZA884744B (en) |
Cited By (16)
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|---|---|---|---|---|
| US6060478A (en) * | 1996-07-24 | 2000-05-09 | Dupont Pharmaceuticals | Azolo triazines and pyrimidines |
| LT4680B (en) | 1996-07-24 | 2000-07-25 | Dupont Pharmaceuticals Company | Azolo triazines and pyrimidines |
| US6191131B1 (en) | 1997-07-23 | 2001-02-20 | Dupont Pharmaceuticals Company | Azolo triazines and pyrimidines |
| US6313124B1 (en) | 1997-07-23 | 2001-11-06 | Dupont Pharmaceuticals Company | Tetrazine bicyclic compounds |
| US6630476B2 (en) | 2000-07-07 | 2003-10-07 | Bristol-Myers Squibb Pharma Company | Pyrrolo [3,4-d] pyrimidines as corticotropin releasing factor (CRF) antagonists |
| US20040176376A1 (en) * | 1999-04-06 | 2004-09-09 | Bristol-Myers Squibb Pharma Company | Pyrazolotriazines as CRF antagonists |
| US20050113375A1 (en) * | 2003-11-25 | 2005-05-26 | Gilligan Paul J. | Salt and crystalline form thereof of a corticotropin releasing factor receptor antagonist |
| US20050143380A1 (en) * | 2003-11-25 | 2005-06-30 | Sherbine James P. | Processes for the preparation of pyrazolo[1,5-a]-1,3,5-triazines and intermediates thereof |
| US6958341B2 (en) | 1999-04-06 | 2005-10-25 | Bristol-Myers Squibb Pharma Company | Pyrazolopyrimidines as CRF antagonists |
| US20060106019A1 (en) * | 2002-07-26 | 2006-05-18 | Greenpharma | Novel substituted pyrazolo[1,5 a]-1,3,5-triazine derivatives and their analogues, pharmaceutical compositions containing same, use thereof as medicine and methods for preparing same |
| US7094782B1 (en) | 1996-07-24 | 2006-08-22 | Bristol-Myers Squibb Company | Azolo triazines and pyrimidines |
| EP0915880B1 (en) * | 1996-07-24 | 2007-10-10 | Bristol-Myers Squibb Pharma Company | Azolo triazines and pyrimidines |
| WO2012087980A1 (en) | 2010-12-21 | 2012-06-28 | Agraquest, Inc. | Sandpaper mutants of bacillus and methods of their use to enhance plant growth, promote plant health and control diseases and pests |
| WO2013039937A1 (en) | 2011-09-12 | 2013-03-21 | Agraquest, Inc. | Methods of enhancing health and/or promoting growth of a plant and/or of improving fruit ripening |
| WO2014139326A1 (en) | 2013-03-13 | 2014-09-18 | Genentech, Inc. | Pyrazolo compounds and uses thereof |
| RU2803728C1 (en) * | 2023-02-15 | 2023-09-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | 3,3'-(1,4-PHENYLENE)BIS(7-[2-{3,4-DIMETHOXYPHENYL}-1-CYANOVINYL]-1,2,3,4-TETRAHYDROPYRAZOLO[1,5-a][1,3,5]TRIAZINE-8-CARBONITRILE) AS ANTIDOTE TO 2,4-D ON SUNFLOWER |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970142A (en) * | 1989-02-16 | 1990-11-13 | Konica Corporation | Silver halide photographic light-sensitive material containing cyan coupler |
| KR20020001958A (en) * | 2000-06-22 | 2002-01-09 | 황성호 | Manufacturing method and composite for sealant which main usage is for protecting preception line of asphalt and cement concrete road |
| DE10116399A1 (en) * | 2001-04-03 | 2002-10-10 | Bayer Ag | Substituted azolazine (thi) one |
| JP5915982B2 (en) * | 2011-04-27 | 2016-05-11 | 国立大学法人静岡大学 | Imidazole derivatives |
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| EP0150974A2 (en) * | 1984-01-26 | 1985-08-07 | The Dow Chemical Company | Novel sulfonamides derived from substituted 2-amino-1,2,4-triazolo(1,5-a)pyrimidines and compositions and methods of controlling undesired vegetation |
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| DE3616681A1 (en) * | 1986-05-16 | 1987-11-19 | Bayer Ag | 1-ARALKYLPYRAZOLE |
-
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- 1987-07-01 DE DE19873722072 patent/DE3722072A1/en not_active Withdrawn
-
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- 1988-06-28 EP EP88110245A patent/EP0297490A1/en not_active Withdrawn
- 1988-06-28 IL IL86901A patent/IL86901A0/en unknown
- 1988-06-29 DD DD88317312A patent/DD285921A5/en unknown
- 1988-06-30 AU AU18564/88A patent/AU606697B2/en not_active Withdrawn - After Issue
- 1988-06-30 US US07/213,905 patent/US4892576A/en not_active Expired - Fee Related
- 1988-06-30 CN CN88104008A patent/CN1030419A/en active Pending
- 1988-06-30 KR KR1019880007968A patent/KR890002154A/en not_active Withdrawn
- 1988-06-30 JP JP63161090A patent/JPS6470489A/en active Pending
- 1988-06-30 SU SU884356000A patent/SU1616507A3/en active
- 1988-06-30 HU HU883386A patent/HUT47393A/en unknown
- 1988-07-01 ZA ZA884744A patent/ZA884744B/en unknown
- 1988-07-01 DK DK368088A patent/DK368088A/en not_active Application Discontinuation
- 1988-07-01 FI FI883168A patent/FI883168A7/en not_active Application Discontinuation
- 1988-07-01 BR BR8803293A patent/BR8803293A/en unknown
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| EP0004171A1 (en) * | 1978-03-10 | 1979-09-19 | Imperial Chemical Industries Plc | Pyrazolotriazinedione derivatives, process for their preparation and herbicidal compositions containing them |
| EP0142152A2 (en) * | 1983-11-14 | 1985-05-22 | The Dow Chemical Company | Novel substituted 1,2,4-triazolo- [1,5-a] pyrimidine-2-sulfonamides and compositions and methods of controlling undesired vegetation and suppressing the nitrification of ammonium nitrogen in soil |
| EP0150974A2 (en) * | 1984-01-26 | 1985-08-07 | The Dow Chemical Company | Novel sulfonamides derived from substituted 2-amino-1,2,4-triazolo(1,5-a)pyrimidines and compositions and methods of controlling undesired vegetation |
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Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060478A (en) * | 1996-07-24 | 2000-05-09 | Dupont Pharmaceuticals | Azolo triazines and pyrimidines |
| LT4680B (en) | 1996-07-24 | 2000-07-25 | Dupont Pharmaceuticals Company | Azolo triazines and pyrimidines |
| US6124289A (en) * | 1996-07-24 | 2000-09-26 | Dupont Pharmaceuticals Co. | Azolo triazines and pyrimidines |
| US6136809A (en) * | 1996-07-24 | 2000-10-24 | Dupont Pharmaceuticals | Azolo triazines and pyrimidines |
| US6358950B1 (en) | 1996-07-24 | 2002-03-19 | Bristol-Myers Squibb Pharma Company | Azolo triazines and pyrimidines |
| US7678793B2 (en) | 1996-07-24 | 2010-03-16 | Bristol-Myers Squibb Pharma Company | Azolo triazines and pyrimidines |
| EP0915880B1 (en) * | 1996-07-24 | 2007-10-10 | Bristol-Myers Squibb Pharma Company | Azolo triazines and pyrimidines |
| US20060252756A1 (en) * | 1996-07-24 | 2006-11-09 | Bristol-Myers Squibb Pharma Company. | Azolo triazines and pyrimidines |
| US7094782B1 (en) | 1996-07-24 | 2006-08-22 | Bristol-Myers Squibb Company | Azolo triazines and pyrimidines |
| US6191131B1 (en) | 1997-07-23 | 2001-02-20 | Dupont Pharmaceuticals Company | Azolo triazines and pyrimidines |
| US6313124B1 (en) | 1997-07-23 | 2001-11-06 | Dupont Pharmaceuticals Company | Tetrazine bicyclic compounds |
| US7026317B2 (en) | 1999-04-06 | 2006-04-11 | Bristol-Myers Squibb Pharma Company | Pyrazolotriazines as CRF antagonists |
| US6960583B2 (en) | 1999-04-06 | 2005-11-01 | Bristol-Myers Squibb Company | Pyrazolotriazines as CRF antagonists |
| US6958341B2 (en) | 1999-04-06 | 2005-10-25 | Bristol-Myers Squibb Pharma Company | Pyrazolopyrimidines as CRF antagonists |
| US20040176376A1 (en) * | 1999-04-06 | 2004-09-09 | Bristol-Myers Squibb Pharma Company | Pyrazolotriazines as CRF antagonists |
| US6734185B2 (en) | 2000-07-07 | 2004-05-11 | Bristol-Myers Squibb Pharma Company | Pyrrolo[3,4-d]pyrimidines as corticotropin releasing factor (CRF) antagonists |
| US6630476B2 (en) | 2000-07-07 | 2003-10-07 | Bristol-Myers Squibb Pharma Company | Pyrrolo [3,4-d] pyrimidines as corticotropin releasing factor (CRF) antagonists |
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| US20090105261A1 (en) * | 2002-07-26 | 2009-04-23 | Greenpharma | Novel substituted pyrazolo[1,5<I>A</I>]-1,3,5-Triazine derivatives and their analogues, pharmaceutical compositions containing same, use thereof as medicine and methods for preparing same |
| US20050113375A1 (en) * | 2003-11-25 | 2005-05-26 | Gilligan Paul J. | Salt and crystalline form thereof of a corticotropin releasing factor receptor antagonist |
| US20070161790A1 (en) * | 2003-11-25 | 2007-07-12 | Bristol-Myers Squibb Pharma Company | Process for the preparation of pyrazolo[1,5-a]-1,3,5-triazines and intermediates thereof |
| US7208596B2 (en) | 2003-11-25 | 2007-04-24 | Bristol-Myers Squibb Pharma Company | Processes for the preparation of pyrazolo[1,5-a]-1,3,5-triazines and intermediates thereof |
| US7442792B2 (en) | 2003-11-25 | 2008-10-28 | Bristol-Myers Squibb Pharma Company | Process for the preparation of pyrazolo[1,5-a]-1,3,5-triazines and intermediates thereof |
| US7153961B2 (en) | 2003-11-25 | 2006-12-26 | Bristol-Myers Squibb Pharma Co. | Salt and crystalline form thereof of a corticotropin releasing factor receptor antagonist |
| US20050143380A1 (en) * | 2003-11-25 | 2005-06-30 | Sherbine James P. | Processes for the preparation of pyrazolo[1,5-a]-1,3,5-triazines and intermediates thereof |
| WO2012087980A1 (en) | 2010-12-21 | 2012-06-28 | Agraquest, Inc. | Sandpaper mutants of bacillus and methods of their use to enhance plant growth, promote plant health and control diseases and pests |
| WO2013039937A1 (en) | 2011-09-12 | 2013-03-21 | Agraquest, Inc. | Methods of enhancing health and/or promoting growth of a plant and/or of improving fruit ripening |
| WO2014139326A1 (en) | 2013-03-13 | 2014-09-18 | Genentech, Inc. | Pyrazolo compounds and uses thereof |
| RU2803728C1 (en) * | 2023-02-15 | 2023-09-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | 3,3'-(1,4-PHENYLENE)BIS(7-[2-{3,4-DIMETHOXYPHENYL}-1-CYANOVINYL]-1,2,3,4-TETRAHYDROPYRAZOLO[1,5-a][1,3,5]TRIAZINE-8-CARBONITRILE) AS ANTIDOTE TO 2,4-D ON SUNFLOWER |
Also Published As
| Publication number | Publication date |
|---|---|
| FI883168A0 (en) | 1988-07-01 |
| BR8803293A (en) | 1989-01-24 |
| FI883168A7 (en) | 1989-01-11 |
| IL86901A0 (en) | 1988-11-30 |
| EP0297490A1 (en) | 1989-01-04 |
| DK368088A (en) | 1989-01-02 |
| HUT47393A (en) | 1989-03-28 |
| AU606697B2 (en) | 1991-02-14 |
| CN1030419A (en) | 1989-01-18 |
| DK368088D0 (en) | 1988-07-01 |
| ZA884744B (en) | 1989-04-26 |
| SU1616507A3 (en) | 1990-12-23 |
| JPS6470489A (en) | 1989-03-15 |
| DD285921A5 (en) | 1991-01-10 |
| KR890002154A (en) | 1989-04-08 |
| DE3722072A1 (en) | 1989-01-12 |
| AU1856488A (en) | 1989-01-05 |
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